Liquid-liquid solvent extraction process



April 6, 1954 R. A. FINDLAY 2,674,563

LIQUID-LIQUID soLvENT ExTRAcTIoN PRocEss Filed Jan. 4. 1950 Patented Apr. 6, 1954 LIQUID -LIQUID i SYOLVENT Y PROCESS;

EXTRACTIONZI.

Robert A. Findlay, Bartlesville, Okla., assigner to Phillips 'Petroleum-Com Delaware f Panna corporation of' Application J anuaryA 4, 1950,;'Serial No..136,7.71.

6 Claims.' (Cl. NGC-11435)" I'his invention relates to the solvent extraction of.,1iqud hydrocarbon materials with liquid solvents In someofits preferred aspects .the invention relates particularlytothe use of mate.- rials which are ordinarily viscous,v as solvents for separating hydrocarbon .materials into fractions of dileringcharacteristics.A In oneof'its preferred embodimentsthe invention relates to particular methods forcontrolling solvent extraction and recovery systems .of .the typedescrbed.

ItV has long been knownthat hydrocarbon.ma-v teria1s,. ordinarily liquidlnixtures of two or more hydrocarbons of different type, 4can beseparated into two or more fractions of differing characteristics by subjecting the mixture inthe liquid phase to contact withcertain polar compounds which act as selective solvents. These selective solvents usually have a greater aflinity for the more cyclic and/or unsaturated hydrocarbons in a series of hydrocarbons of similar molecular weight. The suitability of various polar compounds or mixtures of same as selective solvent for treating a given hydrocarbon mixture varies greatly depending upon the type ofhydrocarbon mixture to be treated and the characteristics of the proposed selective solvent. Thus for a given hydrocarbonmixture, one solvent may be too miscib-le with the mixture, another may be too' nearly immiscible, another may have insuilicient selectivity, another maybe chemically incompatible with a component of the 4hydrocarbon mixture, and. various other deficiencies may `appear which prevent'the useful application of particular solvents.

I have now found that'materials 'which have been proposed as selectiveY solvents but `have not found practical use due lto'ther high .viscosity at ordinary treating temperatures may be employed.

with success by operatingat temperatures con-- siderably above thoseused in most solvent/sys?l tems. This is a phenomenon separate from the known fact that. certain'liquids;- such as. water,-V

which have no'appreciable solvent capacity'can be used at elevated temperatures because the solubility of hydrocarbons therein'v is thus in'- creased.' l have'found that a remarkabler increase in eiciencmusually amounting to several fold; can be attained wtha given solvent'anclv hydrocarbon mixture vina given extraction apjfparatus merely^by employing'a sufficiently high temperature to reduce the viscosity ofthe solvent,

preferably: to belowl four centipoises; during ythe extraction'opera-tion.` A numberofisolv'ents can" be--used in ,thepractice of A.my invention, but two particular solventsgwhich I prefer for treatii'lgr hydrocarbon. mixtures ranging from light gaso-4 lineato gas oilin boiling range, are monoethanolamineand ethylene glycol.. My invention, in its.

more specific.. aspects, lprovides a .very eiective.

onymous terms)- required for introductioninto.

the extraction step.

An object. of this. invention is to effect the separationof aliquid mixture into its components by treating` same. with a solvent selective towards 4fat. least one of said components...

p Anothenobject of the invention is to provide.

an improved. liquidliquid extraction process yfor.

segregating hydrocarbon mixtures into. types.

A further object of the invention is to increase. the eiliciency of extraction severalfold when using a normally viscous solvent.

Yetanother. object of the. invention is to control ,the proportionY of., extracted material separated from the extract phase for return tothe extraction step asfbackwash or stripping fluid.

Another Objectis to supply heat to a selective` solvent in such a mannery that the .heat serves two functions, i. e. separating solvent yfrom `extract and ,effectingextraction atan. elevated tern-vl perature.

A still further. object is.V to providean internal control for; thetemperature of solvent .employed cyclically ina .liquid-liquid extraction process.

Afurther Aobject of the invention is. to .improvev the action ofy monoethanolamine as, a selective solvent inthefseparation of hydrocarbon types.

An additionalobjectof the invention isto improve .the action of. ethylene glycolas a selective solvent in the separation ofhydrocarbon types.

Yfet .another object is to improve .the capacity of a given liquid-liquid extraction` system.

Further. objects andadvantages ,of the invention will become apparent tofthose skilled in the art' from the .accompanying 'disclosure and discussion'. Y

My invention may be"understoodin detail'by reference to the accompanying drawing, which is a schematic flow sheet showing apparatus and flow of materials therethrough suitable for practicing one embodiment of the invention. Certain essential apparatus elements have been shown in diagrammatic form on the flow sheet, but other additional elements have been omitted as they can readily be supplied by one skilled in the art. It will be appreciated that numerous variations from the exact items of apparatus and the particular process described with reference to the accompanying drawing by way of example, may be made without departing from the scope of the invention in its broader aspects.

In the drawing, a hydrocarbon mixture to be separated is drawn from storage or other source not shown via line Ill, is passed through heat exchanger lfs in indirect heat exchange relation with hot extract phase derived as hereinafter described and the thus heated feed is passed via line Hi into extraction column I6 at a point intermediate its ends. My process has wide application, but is most frequently employed in treating hydrocarbon mixtures generally boiling within the gasoline range. highly cracked gasoline having a boiling range of 200 to 250 may be used as feed and separated into a highly aromatic extract and a nonaromatic largely parainic rafnate, the former being employed as blending agent for aviation f gasoline and the latter used in ordinary motor fuel or subjected to catalytic cyclization or other conversion as desired.

The internal structure of extraction column I8 is not shown, as any conventional apparatus now known or developed in the future may be employed so long as it effects intimate contact of solvent with hydrocarbon and permits the ultimate separation of a solvent-rich extract phase and a solvent-poor raiiinate phase. Generally, extraction column iiil will be either of the packed tower type 01' more preferably of the spray type wherein one or more spray nozzles are employed to effect dispersion of one phase into another. One preferred type of column contains packing, and also has a spray nozzle for intimately dispersing hydrocarbon phase into solvent phase.

Into column I6 near its top is introduced a hot stream of solvent via line I8, having a temperature controlled as hereinafter described, which for example may be say 180 F. By way of preferred example the process will be described with particular reference to the use of monoethanolamine as the solvent. Because of the high temperature at which the extraction is effected, the viscosity of the solvent is extremely low and the plate efhciency of extraction column It is from four to six times that found when ordinary atmospheric temperature is used. The liquid solvent flows downwardly through the extraction zone, preferably as the continuous phase, in countercurrent contact with an upwardly flowing, preferably dispersed, hydrocarbon phase. The more aromatic constituents of the feed are dissolved in the solvent and passed downwardly therein in the solvent phase, while the more parainic constituents remain undissolved and pass upwardly in the hydrocarbon phase. Limited amounts of solvent are also dissolved in the hydrocarbon phase. From the top of extraction column DS the hydrocarbon phase. ordinarily called the raffinate phase, is removed via line 2&1. The solvent-rich phase, ordinarily termed the extract phase, is removed from the bottom of column I6 through line 22.

For example, a fraction of a l A portion of the extract phase passes through normally-open valve 24 and line 26 to heat exchanger i2 wherein it is partly cooled by contact with incoming feed. The thus cooled extract phase, after being additionally heat exchanged if necessary in means not shown, passes via line 23 to admixture with the remainder of the extract phase which has passed from line 22 through line 39 and motor valve 32 in an unccoled condition, and the reunited extract phase is then passed through line 34 into settler 36. By virtue of the cooling of part of the extract phase in heat exchanger l2, a portion of the dissolved extract hydrocarbons, aromatic in character, separate out from solution in the solvent-rich extract phase as a separate hydrocarbon phase, which accumulates in the top of settler 36 as phase 38. In the drawing numeral 40 represents the interface between this phase 38 and the remaining extract phase l2 in the lower part of settler 36. Motor valve 32 is controlled by temperature controller M in response to the temperature of the mixed extract phase stream flowing in line 35 detected by a thermocouple d6. Temperature controller le is preset by the operator to give a chosen temperature inline 34 which will effect the separation of the desired proportion of extract as a separate phase 38 in settler 36. This phase is Withdrawn through line 4S by pump 5i) and passed through line 52 into extraction column i6 near the bottom thereof as a stripping fluid, reflux, or backwash, these terms being used synonymously herein, the function of which is to provide additional rectication within the extraction column I6 and insure a high purity extract relatively free from paraffinic components. Pump 5G is controlled by ratecf-fow controller E4 to give a constant feed of extract liquid through line 52 into the extraction column. A liquid level controller 56 is responsive to float 5l to detect the location of interface 40 between hydrocarbon and extract phases in settler 36. When the proportion of extract hydrocarbon being thrown out of solution by virtue of the aforementioned cooling of extract phase changes due to changes in extraction conditions and/ or feed composition, this tends to change the level of interface 4E. At this time liquid level control 5S acts to reset temperature controller M so that the relative proportions of extract phase passing through line 30 without cooling and line 26 with cooling are changed sufiiciently to provide the same quantity of hydrocarbon phase 38 as has previously been chosen and provided.

The extract phase 152 is withdrawn from the bottom of settler 3e and passed via line 58, motor valve 50, and line 62 into a fractionator 54 of conventional design. Fractionator Bil serves to separate the extract hydrocarbons from the solvent. The former, which are lower boiling than the solvent in the case being described, pass overhead as a vapor stream through line 65 and are condensed in condenser 68 as a liquid which flows through line 'it and is then separated into two portions, one being returned through line 'l2 and valve le to the top of the fractionator as reflux and the other being withdrawn through valve 'I6 and line 18 as the extract product of the process.

Heat is added to the bottom of fractionator Ell to effect the necessary rectification therein by heating coil or other suitable device gli, which may be simply a coil placed within the bottom of the fractionator and heated by means of steam or hot oil passed therethrough or which may constitute a separate kettle or reboiler in a manner well known in the art. The solvent, stripped of zeeuwse-i passed`tl1`rou-ghl heat iexchangerv fforf-'adj-ustment of?1 temperature;V additional heat exchange (not shown) iffnecessarygline-86, Vand 4line I tofor returnfto# the topL of extractionfcolumn: I BLK at they choseniele vated temperature suitable forv effecting4 thfe extraction describ'ed.` 'Iheoquantity:A of

heat removed inheat exchanger 84 is controlled by temperature controller 8B which acts in response to atherrnocouple 90"inline 3E, actuating motorvalve |60. The cooledextract phase in line 58 iisrseparated, one-portion movingfthrough..mo-' A tori'rvalve 6I!v andi theother portion passing throughline @Zito heat exchanger 8%3 Yandth'ence throughv line .fill to'join the undiverted-portion'in line 62'for passage to'ffiactionator 64.' Valve St" in line 92 is normally, open; and motor valve iid controlsi the proportion of cooled extract phase which isz-passedrthrougli-.l heatfexchanger to 3 bringtheshot solvent kettle product tothe .chosen temperature for use in extraction column yIii-3f In a mannen similar to that described above with respect to the treatment of the extract phase, .the raiiinate phase Withdrawn from the top of' column It'through line-2t is passed partly through motor-valveBBland partly through .normally opened -valve--Iill)and` line HB2-to heat exchanger IIM, and thence through line IIJ@ to join thevundivertedportion `oiifthe ralinate phase-for iiowi `togetherrthrough line.; I te into fractionator I It;A Infractionatorf-I Ifthefrainate hydrocarbons areiakenoi overhead through line I It, condenser I vI II :and lineal I I, part-being` returned to the togp` offractionaton I I il'iasrfrefluxithrough line I It andzthe balance being-recoveredthrough line I2@ asx, the.` rafiinate.. prod-uctr Fractionator Iii) is heatedgby kettle-heater orreboiler 22, and the relativelyismall quantity; ofsol-Ventwhich is dissolved.infthe;raffinate.phase-isrecovered as a hot bottoms-.product through vline;v I 2t. Thismaterial passes throughheat; exchanger I'illi wherein it is Cooled -to igthe.v properftemperature I( preferably the same asathatiof.A the hot. solvent inline 8e) for use in column IIS, this temperature being detected irrsline.-vv I 2 6F by] thermocouplef I 28` whichI actuates temperature controller.. I 3 Il :which: in lturn ,controls moton` valve,- 98; It' often happens-that the. amount,A ofl solventfwithdrawn in the raffinate phase via lineZBandf-returned to` extractor I6 vialines |215 andllisinsuicient-to make Worthwhile theusesof temperature controller,v 13u, motor.

valvegit; and heatexchanger mitin the manner described. In such, case.these canlbe dispersed 'with as; slight!A variations in the temperature of the solvent being returnedtofthe extraction from the;` .bottom of .ffractionaton III)` willnot alter the heatiinput towextractoril y.enough to cause diiculty in zcontrol..

With monoethanolamine and a gasoline fraction;.suitableztemperatures'for carrying out the extractionzin column. IG-'rangefrom- 170 to 250 l."r Of course sufcient pressure is used to main-A tain the hydrocarbons (and solvent) in liquid phase; At thesetemperatures, thel solubility of the hydrocarbons inthe solventl is increased .considerably overthat at normal atmospheric temperatures and yet the'temperature of complete miscibility'is'notattained; While some decrease in selectivityis encountered because of the increased temperaturepthis is'more. than oiset by the much greater plate. eiciency of extraction colilmnl attained byyirtue of the` lowviscosity offtha solvent .at-lathe; elevated ftemperaturesn. cause of the increased extractionieiiciencytaae Well as the increased hydrocarbon solubility, the throughput ofnjan extraction 1 column'l vI fofv'anyg: given size is considerably increasedwith}',con sequent savings in plant :investment which wouldn be required for a larger extraction apparatus?, While preferred temperatureshaveebeenlmene tioned for certain systems, those.;skilledrinther art having been given the present disclosure will appreciate that optimum temperature will depend on the particular solvent employed and the particular hydrocarbon mixture to be separated. In anygevent, thev temperature should belsuiiiciently highthat thesolventviscosity will be low, much preferably below four centipoises. Flow rates will depend greatly on the extraction apparatus. As indicated above and shown by the'data below; my invention permits theuseof greatlyincreased flow rates in a given extraction systemj., While inonoethanolamine.; andfethylene glycolare my preferred 4solvents;` other .selective solventsA can be'employed, and the invention is ,particularly;` apr..` plicable to those solvents which` aref. atv-usual conditions of operation; too viscous forfeicient operation .of extraction equipment. TheA process of my invention inits various -embodimentsecan be applied-to a large variety of. hydrocarbon mix.. tures containing hydrocarbons of varying degree of saturation whicharefto-be separatedy Such mixturesl are preferably ynorm,ally-liquida ranging from C5 upthrough thefgas oil boilingrange.

Iii-demonstrating the: eiect. of-visco'sity onen-.- extractive solvent on. extraction. column perform,` ance, the y following data? were.- obtained, withthef systeml monoethanolaminecyclohexanewn-hepfV taneat F. and at170 F. Anmunpackedcolf. urn-having a Z-inch inside diameter. wasfusedf, the solvent. beingy introduced near the topl` and thefhydrocarbon feed,v composed of 5l-57weight per cent cyclohexane and49-43;Weightpercent n fh'eptane, was introduced near; .thev bottom,` througha `spray. tip.y Solvent phaseVA wasfwith-rdrawn from .the bottom. Al hydrocarbon-solvent, interface wasmaintained` in the. columnabove'i the point; of. solvent introduction,- andl hydro-.- carbon phase was withdrawn continuously;:from` the top as the rafiinate phase. The; effective heightzof: the column was the dstancenfrom the spray tipY to the interface. In orderftossimulatef. conditions in the central portion: of.' a column.: having sucient stages to obtain complete-sepa.- ration, the solvent introducedl was'first saturated' with hydrocarbon rich in ,n.-heptane thusrepresentingvthe composition ofthe solvent thatv'wouldf be. coming down the column ata point a few' stages. below the top. The hydrocarbon feed' was not presaturated with. solvent since, the lamount of solvent dissolved in the, hydrocarbon, is small, andsince the ratio ofA solventfeedI to.. hydrocarbon feed was high, It will also be noted; that no redux of pure cyclohexane whichwould; be. theextract in: a; column-havingfsuiiicient stages,

` :forcomplete separatiomwas: suppliedtto. therbotr.

tom of the column. The` databelow represent conditions obtaining-in an extraction column be.-. tween the point of hydrocarbon feed. and` alpoint. va few stages below'the top of the columnwhere the raffinate has not yet reached its maximumV purity; butA do notV reflect the` increased separation obtainable with reflux. i'

The following` data show over double the column throughput at. the conditions of solvent.

viscosity below 4 centipoises, as well as increased extraction separation.

System: Monoethnnolamine-cyclohexanen-heptane.

Phase Dispersed: Hydrocarbon dispersed through 0.0138

inch diameter tip.

Column 2-inch I. D. unpacked.

Effective Height: 8.8 feet.

SF: Solvent feed.

HCF: Hydrocarbon feed.

EXT: Extract phase.

RAFF: yRaiiinate phase.

thrown out of solution changes altering said'con-rv Concentrations Flow Solvent Percent Hydrocarbon Percent Ratio 1b. Wt. Percent Cyclohexcne Solvent- Solvent Run Rate Flood In Solvent, Wt. Yield 11i/m. Rate Flb Free Bas Percent lung?? Extraer Weight BF EXT HCF RAFF sr EXT Percent Temperature, 170 F.; Solvent Viscosity, 3.6 centistokes or 3.5 centipoises:

26. l 19. 0 64. 0 5l. 0 36. 5 0. 49 l. 37 0. 2 26. 2 19. 0 64. 2 51. 0 36. 3 0. 49 1. 37 0.3 27. 0 19. 0 66. 1 5l. 0 34. l 0. 49 1. 58 0. 2 4 26. 6 19. 0 6G. l 51. 0 34. l 0. 49 l. 63 0. 4 Temperature, 100 F.; Solvent Viscosity, 11.0 ccntistokes, or 11.1 centiposcs: y 5 13. 8 50 l2. 0 19. 6 57. 7 51. 7 19. 8 72 ll. 8 20. 8 55. 7 51. 7 24. 6 90 l2. 0 18. 4 59. 0 51. 8 27. 5 100 24. 6 90 26. 0 18. 4 50. 7 51. 8

*Column oods at flow rates above 27.5 lb. solvent/hr.

While the invention has been described in detail with respect to various preferred embodiments, those skilled in the art will appreciate that modifications and variations can be made n in the exact details disclosed without departing from the invention. By way of example, in a few instances wherein an exceptionally pure extract is desired, it may be desirable to provide an additional quantity of reflux over that provided from settler 36; this can readily be done by passing a portion of the extract from line 18 into the bottom of extractor I6, either at a constant flow rate or at a rate maintained at a constant ratio to the rate of iiow of liquid in line 48. This and other additions and/or modifications can be made within the scope of the invention.

I claim:

1. An improved process for effecting liquidliquid solvent extraction with relatively viscous solvents which comprises intimately contacting such a solvent at a temperature suciently elevated to give a solvent viscosity of not above four centipoises with a hydrocarbon mixture containing components of differing solubility in said solvent, at suicient pressure to maintain the solvent and hydrocarbons in liquid phase, withdrawing a solvent-poor raffinate phase from said contacting, withdrawing a solvent-rich extract phase from said contacting, passing a portion of said extract phase in heat exchange with cold hydrocarbon mixture passed to said contacting, passing the remaining portion of said extract phase into admixture with thus cooled extract phase and eecting separation of a resulting solvent enriched extract phase from a liquid hydrocarbon phase comprising extract hydrocarbons thrown out of solution by said cooling, returning the thus separated extract hydrocarbon phase to the said contacting as reiiux at a constant rate of ow, controlling the relative proportions oi' extract phase cooled by said heat exchange and not cooled by said heat exchange to produce a mixture of same having a constant temperature, whenever the quantity of separated extract phase reux and recovering the remainder as extract product of the process, heating the bottom of said ractional distillation zone to eect stripping of extract hydrocarbons from solvent therein and to produce a hot solvent bottoms product, passing the latter to said heat exchange step for heat exchange with the aforesaid portion of solvent enriched extract phase, controlling the relative proportions of said extract phasev (a) passed to said heat exchange step and thence to said fractionator and (b) passed direct to said fractionator without heat exchange, to cool said hot solvent to a constant tempera-ture for introduction into said extraction step, and recovering from said rafnate phase raninate hydrocarbons as a product of the process.

2. A process according to claim 1 wherein said solvent poor rainate phase is passed to different but corresponding fractional distillation zone and heat exchange step and wherein the resulting hot solvent is correspondingly cooled to the same constant temperature by controlling the relative proportions (2) and (b) of said rafnate phase.

3. A process according to claim 1 wherein said solvent is monoethanolamine.

4. A process according to claim 1 wherein said solvent is ethylene glycol.

5. A process according to claim 1 wherein said solvent is monoethanolamine and said extraction is effected at a temperature within the range of 170 to 250 F.

(i. An improved process for effecting liquidliquid solvent extraction with relatively viscous solvents which comprises intimately contacting such a solvent at a temperature suiiiciently elevated to give a solvent viscosity of not above four eentipoises with a hydrocarbon mixture containing components of differing solubility in said solvent, at sumcient pressure to maintain the solvent and hydrocarbons in liquid phase, withdrawing a solvent-poor raflinate phase from said contacting, withdrawing a solvent-rich extract phase from said contacting, passing a portion of said extract phase in heat exchange with cold hydrocarbon mixture passed to said contacting,

9 passing the remaining portion oi said extract phase into admixture with thus cooled extract phase and effecting separation of a resulting solvent enriched extract phase from a liquid hydrocarbon phase comprising extract hydrocarbons thrown out of solution by said cooling, returning the thus separated extract hydrocarbon phase to the said contacting as reflux at a constant rate of ilow, controlling the relative proportions of extract phase cooled by said heat exchange and not cooled by said heat exchange to produce a mixture of same having a constant temperature, whenever the quantity of separated extract phase thrown out of solution changes altering said constant temperature to maintain said quantity un- 15 changed.

10 References Cited in the file of this patent UNITED STATES PATENTS Number- Name Date 1,776,550 Clark et al Sept. 23, 1930 2,246,297 Duncan et al June 17, 1941 2,337,732 Burk et al Dec. 28, 1943 2,400,802 Arnold May 21, 1946 OTHER REFERENCES Kalichevsky: Modern Methods of Rening Lubricating Oils, Reinhold Publishing Co. (1938), pages 116. 121. 

